Metal phthalocyanine dyestuffs



l I Ice 3,287,470

Patented Nov. 22, 1966 United States Patent Alkylene represents the1,2-ethylene or the 1,2- or 3,287,470 1,3-propylene radical.

z g fi figgg figsgg m gy figfi 1 Because of its high stability andpurity of shade, copper switzerlgn assigliors to J I" g s 222phthalocyanine tetrasulphonic acid chloride is preferably Switzerland 5used as metal phthalocyanine tetrasulphonrc acid halide. No DrawingFiled July 1 1963 set. No. 292,104 1 However, the corresponding nickeland cobalt phthalocy- Claims Priority, application Switzerland July1962, anine sulphonic acid chlorides have also been used. The

sulphonic acid chloride groups are in the 4- and/or in 7 Claims. (Cl.260-3145) the 3-positions depending on whether, in the production 10thereof, 4-sulphophthalic acid is used as starting material The presentinvention relates to new metal phthalocya- Whether the groups areintroduced y Subsequent $111 nine dyestuffs which are soluble inacetone, a process for Phoflation y diffict sulphochlorination of the pthe production thereof, their use for the dyeing of high y Thephthalocyanines can be further Substituted, molecular hydrophobicorganic material in the mass and, for eXample, y maximally foulhalogens, instance a i du t i l rod ct, th t i fl d d h ith chlorine orbromine atoms per molecule. The use of as It is one of the objects ofthe invention to provide new P as Possible PP Phthzllmyaninetetrasulphonic metal phthalocyanine dyestuffs which are more readilyacid Chlorideis ecomme ded.

filtrable than the known dyestuffs of this class and which Examples ofamines of Formula I which are suita e i are consequently better suitablefor the spinning of, espethe Production of the dyestuffs of Formula 11according cially, dyed-in-the-mass acetyl cellulose and the like fibers.t t e nt n a yl n g yee1-O-methy ethylene In conventional spinning ofsuch acetylcellulose, speg Y Y ethylene g1yco1-O-propy1-, ethyleneglycolcial, cumbersome precautions must be taken against a y '-(l m y I'-('Y- P PY clogging up of the spinnerets. To prevent this from ether ordiethylene glycol-O-methyb, diethylene glycol-O- occurring, thephthalocyanine dyestulf containing acetone ethylor diethyleneglycol-O-butyl-O'-(fi-aminoethyl) or solution is filtered separately,the cellulose solution '-('Y- -P PY h (acetyl cellulose) is filteredseparately, and the filtrates An improvement in the solubilityproperties of the end from these two operations are mixed with eachother and product is particularly attained by using mixtures of such themixture must again be subjected to usually several amines in theproduction of the dyestuffs of Formula H. filtration steps, namely atleast one after mixing and a These amines are obtained, for example, byadding second one immediately prior to feeding of the mixtureacrylonitrile or acrylamide to the corresponding alkylene to thespinnerets. glycol or dialkylene glycol monoalkyl ethers and subse- Ithas been found that new metal phthalocyanine dyequently hydrogenatingthe nitrile compound obtained, or stuffs which are particularly easilysoluble in acetone are by degradation of the amide according toHoffmann, or obtained by reacting one mole of a metal phthalocyanine byreaction of the corresponding chloroor sulpho-ester tetrasulphonic acidhalide with 4 mols of an amine of the derivatives with ammonia. f r ulaThe dyestuffs of Formula 11 according to the invention dissolve with ablue to greenish blue colour in organic HzN-aIkyIene-O-(aIk lBne-O Asolvents such as esters and, particularly, in ethanol and (I) inacetone. They are suitable for the dyeing of natural wherein 49 orsynthetic resins, waxes, lacquers such as nitro or stoving alkylenerepresents an alkylene radical having cap lacquers, and plastic massese.g. of cellulose ethers or bon atoms esters, in particular for thedyeing of acetyl cellulose in A represents an alkyl radical, preferablyof 1 to 12 carbon the mass as Wen fol. the dyemg of natural or syntheticatoms and polymers or condensation products. Above all, synthetic xrepresents 1 or 2 rayon can be dyed by the spin dyeing method in clearblue shades with the dyestuffs according to the invention. T he and therecurring alkylene groups can be the same or dyeings are fast tochlorine, industrial fumes and light. different from each other, or byreacting one mole of the A spinning mass of acetyl cellulose in acetonecontaining aforesaid halide with, in all, four moles of a mixture ofmetal phthalocyanine dyestuffs according to the invention several, e.g.two, three or four amines of Formula I 50 can be much more easilyfiltered and there is thus much to form a metal phthalocyanine dyestulfof the formula less tendency to clog the spinnerets than there is with L.l. A40-(CH2)z]-O(CH2)uNH"*SO SOPNH .('CHI)D-O [(CH2)q O 'A| L a Is (It)wherein dyestuffs containing the previously known phthalocyaninecompounds of a similar constitution.

In comparative filtration tests under identical conditions of pressureand filter composition, the dyestulfs of Formula II passed the filterfive to ten times more rapidly than the corresponding dyestulfs of theformula Pc is a metal phthalocyanine complex dyestufl radical in whichthe metal is copper, nickel or cobalt, each of A A A and A independentlyis alkyl with preferably from 1 to 12 carbon atoms, each of a, b, c andd, independently, is an integer ranging from 1 to 2, and A;;O-(CHz)-NHSOi SOzNH(CHl)mOA each of m, n, p, q, r, s, t and u, takenindependently is an integer ranging from 2 to 3. In the dyestuif ofFormula II the four sulphamide groups are thus the same, or differentfrom each other, wherein A A A A.,,, m, p, s, u and Po have themeandepending on the number of amines reacted with the 'ings given underFormula II. aforesaid halides. Further details can be seen from thefollowing nonlimitative examples The temperatures are in degreescentigrade, .g..stands.for gram," ml. for milliliteri -P ercentages andparts areby weight unless stated otherwise.

Example I Y 38.8 g. of. copper phthalocyanineytetrastilphonic acidchloride as 20%-aqueous paste are suspended'in 200g. of ice and 200ml.of water and .47 g. of ethylene glycol--ethyl-O,-('y-;amino-propyl)-di-ether are added. The pH of the suspensionthen rises to 10.8. After stirring for 1 hour, 40 mlsofa Z-N sodiumacetate solution are added to the suspension. After stirring for .16hours at room temperature, during which time the pH decreases to 9.2,

the blue suspension :is filtered, the residue is washed with water anddried. 42.5 g. of a blue product which is solu-. ble in' acetoneareobtained. The product is very well suited for the dyeing of acetylcellulose in the mass. Blue.dyestufis having similarly good solubilitypropertiesare obtained by using in the process described in the aboveexample, instead of ethylene glycol-O-ethyl-O'- -aminopropyl)-di-ether,42.5 g. of ethylene glycol-O- methyl-Qf-(y-aminopropyl)-di-ether or 56g. of ethylene glycol-O-butyl-O'-('y-aminopropyl)-di-ether or 42.5 g..of ethylene glycol-O-ethyl-O'-(B-aminoethyl)-di-ether or 92 g. ethyleneglycol-O-dodecyl-O'-('y-aminopropyl) -di-ether or 61 g. of diethyleneglycol-O-ethyl-O'-('y-aminopropylh tri-ether or 42.5 g. of ethylene'glycol-O-butyl-U-(B- minoethyD-di-ethcr.

More greenish dyestuffs having similar properties are also obtained byusing, instead of copper phthalocyanine tetrasulphonic acid chloride,the same amounts of nickel or cobalt phthalocyaninetetrasulphonic acidchloride, and otherwise following the procedure given in the aboveexample. I a V The starting metalphthalocyanine tetrasulphonic acidchlorides are producedbyheating for 4 hours the respective metalphthalocyanine in 12 -times the amount of chlorosulphonic acid at140-142", treating this solutionv I for'2 hours with 1.5 timesthe amountof thionyl' chloride at 75-80 (calculated on, the metal phthalocyanine),precipitating the metal phthalocyanine tetrasulphonic acid chloride onice and water, filtering oil-and'washing thev residue with cold wateruntil the Washing water is neutral to Congo-paper. I When, in thisexample,

Erample 38.3 g. of the copper phthalocyanine tetra sulphonic acid 60 ofwater and a mixture of 23.5 g. of ethylene glycol-O'-- chloride,produced as described in Example 1, as a 20%- aqueous paste aresuspended in 200 g. of ice and 200 ml.

('y-aminopropyl) -di-ether and 28 g. of ethylene glycol-O- butyl- Q'-('-aminopropyl) di-ether is added. The' pH of the suspension rises to10.5: After stirring for 1 hour, 40ml. of 2-N sodium acetate solutionare added to the suspension.- After stirring for 16 hours at roomtemperature, whereby the pH decreases to 9.2, the blue suspension isfiltered and the residue iswashed with water and dried;

a mixture of 11.65 g. of ethylene;glycol-O-methyl-0?;(y-aminbpropyl)-di-ether, 12.75 g. of.

44.6 g. of a blue acetone-soluble product are obtained which'is verywell suited for the dyeing of acetyl cellulose in the mass.

Example 3 38.8 g. of 4,4',4",4-copper phthalocyanine tetrasulphonic:acid chloride, as 20% aqueous paste, are suspended in 200 g. of ice and200 ml. of water and 47 g. of

. ethylene glycol-O-ethyl-O'-('y-aminopropyly)-di-ether are all 35.8 g.of 4,4',4",4"'-co pper phthalocyanine tetrasuh phonic acid (producedfrom 4-sulphophthalic acid anhydi'ide), in 360 g. of chlorosulphonicacid for 2 hours, treating this solution with 54 g of thionyl chloridefor 2 hours at, 75,80, precipitating the 4,4',4'.',4"'-copperphthalocyanine tetrasulphonic acid chloride onto ice and.

into a current of air.

v 'vatei, filtering and washing theresidue with cold water.

Example 4 l 9" g. of nitrocellulose of medium viscosity, 3 g.'of

phthalic acid dibutyl ester and 18 gof coconut oil 30 fatty acidmodified alkyd resin (consisting of 40% ofv coconut-fatty acid, 39%phthalic acid anhydride andv 21% of dimethylol propane), are dissolvedin 24.5 g. of butyl acetate,'17.5 g. of ethyl acetate, 24.5 g. oftoluone and 2.1g. of butanol and 1.4 g. of 2 ethoxy-ethanol. A solutionof 0.5 g.'of the dyestuif produced according to Example 1 from copperphthalocyanine tetrasulphonic acid chloride and ethyleneglycol-O-ethyl-O'-('y-aminopropyl)-ether in 10 g. of ethylene glycolmonoethyl ether is added. After homogeneously mixing, this lacquer issprayed onto aluminium sheet and dried in the air. A pure blue dyeing ofgood fastness to light is obtained.

Example 5 6.25 g. of Z-ethoxy-ethanol, 6 g. of a ketone formalde hydecondensation resin and 10 g. of the dyestuifproduced according toExample l'from copper phthalocyanine tetrasulphonic acid chloride andethylene glycol-( buty1-O"-(' -aminopropyl)-di-ether, are dissolved in26 g. of ethylene glycol monomethyl ether and 49.. g. of

ethyl alcohol and 3 g. of trixylyl phosphate are added. This easilyflowing printing colour is printed onto aluminium sheets by the intaglioprinting process or the flexographic process. ,Brilliant blue printshaving good fastness to light and water are obtained.

Example 6 n 1.3 g. of the-dyestuif produced according to Example, 1 fromcopper phthalocyanine tetrasulphonic acid chloride and ethyleneglycol-O-butyl-O'-(fl-arninoethyl)-diether and 260 g. of acetylcellulose are dissolved while stirring in 740 g. of acetone. Thissolution is then pumped with the aid of a gear pump through nozzles Inthis spinning process the nozzles are not clogged. Pure blue acetylcellulosefibres- Til-5h obtained which have very good fastness to wetand 'Weclainn' y 1. Metal phthalocyanine dyestuffs of the formula 5wherein Pc is a metal phthalocyanine complex dyestufr' radical in whichthe metal is a member selected from the group consisting of copper,nickel and cobalt, each of A A A and A independently, is alkyl with from1 to 12 carbon atoms, each of a, b, c and d, independently, is aninteger ranging from 1 to 2, each of m, n, p, q, r, s, t and u, takenindependently, is

an integer ranging from 2 to 3. 2. A metal phthalocyanine dyestufiaccording to claim 1 wherein said metal is copper.

3. The copper phthalocyanine dystufi of the formula wherein Fe is copperphthalocyanine residue.

4. The copper phthalocyanine dyestufi of the formula wherein Fe iscopper phthalocyanine residue.

5. The copper phthalocyanine dyestufi of the formula wherein Fe iscopper phthalocyanine residue.

6. The copper phthalocyanine dyestufi of the formula Pc[SO NH-CH CH OCHCH OCH CH wherein Fe is copper phthalocyanine residue.

7. The copper phthalocyanine dyestuif of the formula JOHN D. RANDOLPH,Primary Examiner.

J. A. PATTEN, Assistant Examiner.

1. METAL PHTHALOCYANINE DYESTUFFS OF THE FORMULA WHEREIN PC IS A METALPHTHALOCYANINE COMPLEX DYESTUFF RADICAL IN WHICH THE METAL IS A MEMBERSELECTED FROM THE GROUP CONSISTING OF COPPER, NICKEL AND COBALT, EACH OFA1, A2, A3 AND A4, INDEPENDENTLY, IS ALKYL WITH FROM 1 TO 12 CARBONATOMS, EACH OF A, B, C AND D, INDEPENDENTLY, IS AN INTEGER RANGING FROM1 TO 2, EACH OF M, N, P, Q, R, S, T AND U, TAKEN INDEPENDENTLY, IS ANINTEGER RANGING FROM 2 TO 3.